JP4502674B2 - Method for separating phosphorus-containing material from spent catalyst - Google Patents

Method for separating phosphorus-containing material from spent catalyst Download PDF

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JP4502674B2
JP4502674B2 JP2004082979A JP2004082979A JP4502674B2 JP 4502674 B2 JP4502674 B2 JP 4502674B2 JP 2004082979 A JP2004082979 A JP 2004082979A JP 2004082979 A JP2004082979 A JP 2004082979A JP 4502674 B2 JP4502674 B2 JP 4502674B2
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phosphorus
nickel
vanadium
molybdenum
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仁美樹 矢野
公司 小池
誠人 杉本
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日本キャタリストサイクル株式会社
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description

本発明は、各種石油留分の水素化脱硫に使用された触媒からリン含有物を分離する方法に関する。   The present invention relates to a method for separating phosphorus-containing materials from a catalyst used for hydrodesulfurization of various petroleum fractions.

従来、各種石油留分の水素化脱硫触媒として、モリブデンやニッケル等が使用されている。また、水素化脱硫触媒には、使用中に石油留分に含まれていたバナジウムやニッケルが付着する。近年、水素化脱硫触媒性能を向上させるため、リンを添加する方法が用いられている。触媒の高性能化に伴い、リンを添加した触媒の量及びその添加量は増加している。   Conventionally, molybdenum, nickel, and the like have been used as hydrodesulfurization catalysts for various petroleum fractions. Further, vanadium and nickel contained in the petroleum fraction during use adhere to the hydrodesulfurization catalyst. In recent years, a method of adding phosphorus has been used in order to improve the hydrodesulfurization catalyst performance. As the performance of the catalyst increases, the amount of the catalyst to which phosphorus is added and the amount added are increasing.

触媒性能が低下して交換された使用済触媒からの、バナジウム、モリブデン、ニッケル等の有価金属の回収方法として、使用済触媒にナトリウム化合物を添加し、６００℃以上の温度で焙焼して、モリブデンやバナジウムを水溶性塩にし、さらに、焙焼物を水で浸出することにより、モリブデンやバナジウムを製品化するための始液を得る方法が用いられている（例えば、特許文献１、非特許文献１及び２参照）。
特開平５−１５６３７５号公報 須藤欽吾,「使用済水素化脱硫触媒よりの金属リサイクリング」,燃料協会誌,第６９巻,第１１号（１９９０年）,Ｐ.１０４２−１０４５ 小野浩昭,「使用済脱硫触媒からの金属の抽出」,分離技術,第２５巻,第２号（１９９５年）,Ｐ.３３−３６ As a method for recovering valuable metals such as vanadium, molybdenum, nickel, etc., from a used catalyst that has been replaced due to reduced catalyst performance, a sodium compound is added to the used catalyst and roasted at a temperature of 600 ° C. or higher. A method of obtaining an initial solution for commercializing molybdenum or vanadium by making molybdenum or vanadium into a water-soluble salt and leaching the roasted product with water is used (for example, Patent Document 1, Non-Patent Document). 1 and 2).
JP-A-5-156375 Jun Sudo, "Metal recycling from spent hydrodesulfurization catalyst", Journal of Fuel Association, Vol. 69, No. 11 (1990), p. 1042-1045 Ono Hiroaki, “Extraction of Metals from Used Desulfurization Catalysts”, Separation Technology, Vol. 25, No. 2 (1995), P.33-36

上記従来方法において、使用済触媒中にリンを含有する場合、リンの大部分はニッケルと共に残渣中に留まる。このニッケル含有残渣は、フェロニッケルの原料として使用されているが、リンを含有する場合は、製品のフェロニッケル中にリンが分配するので好ましくない。   In the above conventional method, when phosphorus is contained in the spent catalyst, most of the phosphorus remains in the residue together with nickel. This nickel-containing residue is used as a raw material for ferronickel. However, when phosphorus is contained, it is not preferable because phosphorus is distributed in the ferronickel of the product.

ところで、フェロニッケル製品規格中にはリン含有量の規定があり、ニッケル含有残渣の使用量は制約を受けている。フェロニッケル原料としての使用量を増加させるには、ニッケル含有残渣中のリンを分離除去する必要がある。   By the way, in the ferronickel product specification, there is a regulation of phosphorus content, and the amount of nickel-containing residue used is restricted. In order to increase the amount used as a ferronickel raw material, it is necessary to separate and remove phosphorus in the nickel-containing residue.

本発明は、上記の実情に鑑みてなされたものであり、その目的は、使用済触媒からリン含有物を分離する方法を提供することにある。   This invention is made | formed in view of said situation, The objective is to provide the method of isolate | separating a phosphorus containing material from a used catalyst.

上記の目的を達成するため、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をｐＨ６から９の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とする。
In order to achieve the above object, the method for separating phosphorus-containing material from the spent catalyst according to the present invention was used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium . A spent catalyst using alumina as a carrier and a roasted product obtained by baking a sodium compound at a temperature of 600 ° C. or higher are acid leached at a pH of 5 or lower, filtered, and nickel-containing with a low phosphorus content The residue is separated into a filtrate, and the filtrate is further adjusted to pH 6 to 9 to neutralize and precipitate phosphorus, aluminum, etc., and filtered to obtain a vanadium and / or molybdenum product starting solution, It is characterized by separating into phosphorus-containing starch.

また、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ６から９で浸出し、これを濾過して、ニッケル含有残渣とモリブデン及び/又はバナジウム製品化始液とに分離し、前記ニッケル含有残渣をｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をｐＨ６から９の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とする。
In addition, the method for separating phosphorus-containing material from the spent catalyst according to the present invention is a method of using alumina used as a carrier for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. The baked product obtained by roasting the spent catalyst and sodium compound at a temperature of 600 ° C. or higher was leached at pH 6 to 9, and filtered to obtain a nickel-containing residue and molybdenum and / or vanadium product starting solution. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue having a low phosphorus content and a filtrate, and the filtrate is adjusted to a pH between 6 and 9. And neutralizing and precipitating phosphorus, aluminum, etc., and filtering this to separate into vanadium and / or molybdenum product starting solution and phosphorus-containing starch.

また、本発明による使用済触媒からリン含有物を分離する方法は、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ１０以上でアルカリ浸出し、これを濾過して、ニッケル含有残渣と濾液とに分離し、更に、前記ニッケル含有残渣をｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、前記各濾液をｐＨ６から９に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、モリブデン及び/又はバナジウム製品化始液と、リン含有澱物とに分離することを特徴とする。
In addition, the method for separating phosphorus-containing material from the spent catalyst according to the present invention is a method of using alumina used as a carrier for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. The baked product obtained by roasting the spent catalyst and the sodium compound at a temperature of 600 ° C. or higher is alkali leached at a pH of 10 or higher, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue and a filtrate having a low phosphorus content. The filtrates are adjusted to pH 6 to 9, and phosphorus, aluminum, and the like are contained therein. It is characterized in that it is precipitated and filtered to separate into molybdenum and / or vanadium product starting liquid and phosphorus-containing starch.

本発明によれば、使用済触媒から効率良くリン含有物を分離することができ、延いては、リン含有量の低いフェロニッケル原料等を提供することができる。   According to the present invention, it is possible to efficiently separate a phosphorus-containing material from a used catalyst, and thus it is possible to provide a ferronickel raw material having a low phosphorus content.

本第１の発明によるニッケル含有残渣中のリンの分離除去は、図１に示す通り、バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をｐＨ６から９の間に調整して、これを濾過して、リン及びアルミニウム及びリン含有澱物と、バナジウム及び/又はモリブデン製品化始液に分離することにより行なわれる。
As shown in FIG. 1, the separation and removal of phosphorus in the nickel-containing residue according to the first aspect of the present invention is the use of alumina used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium. A nickel-containing residue having a low phosphorus content is obtained by acid leaching a spent catalyst obtained by using a catalyst as a carrier and a roasted product obtained by baking a sodium compound at a temperature of 600 ° C. or higher at pH 5 or lower, and filtering this. In addition, the filtrate is adjusted to pH 6-9 and filtered to separate phosphorus and aluminum and phosphorus-containing starch and vanadium and / or molybdenum product starting solution. Is done.

水素化脱硫触媒の担体はアルミナである。一方、使用済触媒中のニッケルは、硫化物もしくは酸化物として存在している。焙焼により、ニッケル硫化物は酸化されて酸化物となる。ニッケル酸化物とアルミナは、反応してニッケルアルミネートとなる。また、アルミナの大部分は、アルファ・アルミナとなり、ニッケル及びアルミニウムは、浸出し難い化合物形態となる。一方、リンの大部分は、リン酸ナトリウム、リン酸アルミニウム、リン酸カルシウム等の形態で焙焼物中に存在する。   The support for the hydrodesulfurization catalyst is alumina. On the other hand, nickel in the used catalyst exists as sulfide or oxide. By roasting, the nickel sulfide is oxidized to an oxide. Nickel oxide and alumina react to form nickel aluminate. Further, most of alumina becomes alpha-alumina, and nickel and aluminum are in a compound form that hardly leaches. On the other hand, most of phosphorus is present in the roasted product in the form of sodium phosphate, aluminum phosphate, calcium phosphate or the like.

カルシウムの含有量に差のある２種類の使用済触媒に炭酸ナトリウムを加え、９００℃で焙焼した焙焼物のＩＣＰ分析値を下表１に示す。使用済触媒中にカルシウムが含まれている場合は、ｐＨ５以下で酸浸出するのが効果的である。これにより、リン酸カルシウムも浸出することができる。一方、使用済触媒中のカルシウムが少ない場合は、アルミニウムやニッケルの浸出量の減少するｐＨ１０以上で浸出するのが効果的である。
Table 1 below shows ICP analysis values of the baked product obtained by adding sodium carbonate to two kinds of used catalysts having different calcium contents and baking at 900 ° C. If it contains spent catalyst mosquito Le Siumu in, it is effective to acid leaching at pH5 or less. Thus, it is possible to leach phosphorylation Le Siumu. On the other hand, if the mosquito Le Siumu in the spent catalyst is small, leaching of aluminum and nickel leaching of decreasing pH10 or more is effective.

表１
Table 1

また、本第２の発明によるニッケル含有残渣中のリンの分離除去は、図２に示す通り、上記焙焼物をｐＨ６から９で浸出し、これを濾過して、ニッケル含有残渣とモリブデン及び/又はバナジウム製品化始液とに分離し、このニッケル含有残渣をｐＨ５以下で酸浸出し、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、この濾液をｐＨ６から９の間に調整して、濾過し、リン及びアルミニウム含有澱物と、バナジウム及び/又はモリブデン製品化始液とに分離することにより行なわれる。
Further, the separation and removal of phosphorus in the nickel-containing residue according to the second aspect of the present invention is carried out by leaching the roasted product at pH 6 to 9 and filtering it, as shown in FIG. The nickel-containing residue is acid leached at a pH of 5 or less, separated into a nickel-containing residue having a low phosphorus content and a filtrate, and the filtrate is adjusted to a pH between 6 and 9. Filtration and separation into phosphorus and aluminum containing starch and vanadium and / or molybdenum product starting liquor.

この場合、濾液へのリンやアルミニウム浸出量は少なく、濾液をモリブデン、バナジウム製品化始液とすることができる。一方、ニッケル含有残渣中のリンを分離除去しなければならない。上記と同様、使用済触媒中にカルシウムが含まれている場合は、ｐＨ５以下で酸浸出するのが効果的であり、使用済触媒中のカルシウムが少ない場合は、ｐＨ１０以上で浸出するのが効果的である。
In this case, the amount of leaching of phosphorus and aluminum into the filtrate is small, and the filtrate can be used as a molybdenum or vanadium product starting solution. On the other hand, the phosphorus in the nickel-containing residue must be separated and removed. As described above, if it contains a mosquito Le Siumu in the spent catalyst is effective is to acid leaching at pH5 or less, when mosquito Le Siumu in the spent catalyst is small, leaching at pH10 or It is effective to do.

さらに、本第３の発明によるニッケル含有残渣中のリンの分離除去は、図３に示す通り、上記焙焼物をｐＨ１０以上でアルカリ浸出し、濾過し、ニッケル含有残渣と濾液とに分離し、更に、ニッケル含有残渣をｐＨ５以下で酸浸出し、濾過し、リン含有量の低いニッケル含有残渣と濾液とに分離し、前記各濾液をｐＨ６から９に調整して、濾過し、アルミニウム及びリン含有澱物とモリブデン、バナジウム製品化始液とに分離することにより行なわれる。
Further, the separation and removal of phosphorus in the nickel-containing residue according to the third aspect of the invention, as shown in FIG. 3, the baked product is alkali-leached at a pH of 10 or more, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue and a filtrate having a low phosphorus content, and each filtrate is adjusted to a pH of 6 to 9 and filtered to obtain an aluminum and phosphorus-containing starch. By separating the product into molybdenum and vanadium product starting solution.

この場合も、得れた焙焼物をｐＨ５以下で酸浸出し、濾過し、ニッケル含有残渣と濾液とに分離する。ニッケル含有残渣を、更にｐＨ１０以上でアルカリ浸出する。また、最初にｐＨ１０以上でアルカリ浸出したニッケル含有残渣を、更にｐＨ５以下で酸浸出しても、同様にリン含有量の低いニッケル含有残渣を得ることができる。   Also in this case, the obtained roasted product is acid leached at pH 5 or less, filtered, and separated into a nickel-containing residue and a filtrate. The nickel-containing residue is further alkaline leached at a pH of 10 or higher. Further, even when the nickel-containing residue initially leached with alkali at pH 10 or higher is further acid leached at pH 5 or lower, a nickel-containing residue having a low phosphorus content can be obtained.

以下、本発明の実施例を説明する。
上記表１の焙焼物Ａ、Ｂ各々３０ｇをイオン交換水１５０ｍｌに浸し、水酸化ナトリウム溶液でｐＨ８.０に調整しながら５０℃で６０分浸出し、５Ｃ濾紙で濾過した。更に、得られた残渣をイオン交換水５０ｍｌで洗浄濾過し、ＩＣＰ分析した。以上の結果を、下表２に示す。残渣には、リンが焙焼物Ａで０.７２乾燥重量％、焙焼物Ｂで０.６９乾燥重量％残留した。 Examples of the present invention will be described below.
30 g of each of the baked products A and B shown in Table 1 above were immersed in 150 ml of ion-exchanged water, leached at 50 ° C. for 60 minutes while adjusting to pH 8.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the obtained residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. The above results are shown in Table 2 below. In the residue, 0.72% by weight of phosphorus remained in the roasted product A and 0.69% by dry weight of the roasted product B remained in the residue.

表２
Table 2

実施例１
表１の焙焼物Ａ、Ｂ各々３０ｇをイオン交換水１５０ｍｌに浸し、水酸化ナトリウム溶液でｐＨ１２.０に調整しながら５０℃で６０分浸出し、５Ｃ濾紙で濾過した。更に、得られた残渣をイオン交換水５０ｍｌで洗浄濾過し、ＩＣＰ分析した。同様に、イオン交換水１５０ｍｌに浸し、硫酸溶液でｐＨ１.５に調整しながら浸出した。以上の結果が表２に示されている。焙焼物Ａの場合、ｐＨ１２.０よりｐＨ１.５の方がリンの除去分離効果が大きい。
一方、カルシウムの少ない焙焼物Ｂにおいては、ｐＨ１２.０とｐＨ１.５に差はなかった。
Example 1
30 g of each of the baked products A and B shown in Table 1 were immersed in 150 ml of ion-exchanged water, leached at 50 ° C. for 60 minutes while adjusting to pH 12.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the obtained residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. Similarly, it was immersed in 150 ml of ion exchange water and leached while adjusting to pH 1.5 with a sulfuric acid solution. The above results are shown in Table 2. In the case of the baked product A, the removal and separation effect of phosphorus is greater at pH 1.5 than at pH 12.0.
On the other hand, in the small roasting product B of mosquitoes Le Siumu was no difference pH12.0 and pH 1.5.

実施例２
表１の焙焼物Ａ、Ｂ各々３０ｇをイオン交換水１５０ｍｌに浸し、水酸化ナトリウム溶液でｐＨ８.０に調整しながら５０℃で６０分浸出し、５Ｃ濾紙で濾過した。更に、残渣をイオン交換水５０ｍｌで洗浄濾過し、残渣を得た。この残渣をイオン交換水１５０ｍｌに浸し、水酸化ナトリウム溶液でｐＨ１２.０に調整しながら５０℃で６０分浸出し、５Ｃ濾紙で濾過した。更に、残渣をイオン交換水５０ｍｌで洗浄濾過し、ＩＣＰ分析した。同様に、ｐＨ８.０の浸出残渣をイオン交換水１５０ｍｌに浸し、硫酸溶液でｐＨ１.５に調整しながら浸出した。以上の結果が表２に示されている。焙焼物Ａの場合、ｐＨ１２.０よりｐＨ１.５の方がリンの除去分離効果が大きい。
一方、カルシウムの少ない焙焼物Ｂにおいては、ｐＨ１２.０とｐＨ１.５に差はなかった。 Example 2
30 g of each of the baked products A and B shown in Table 1 were immersed in 150 ml of ion-exchanged water, leached for 60 minutes at 50 ° C. while adjusting to pH 8.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Furthermore, the residue was washed and filtered with 50 ml of ion exchange water to obtain a residue. This residue was immersed in 150 ml of ion-exchanged water, leached for 60 minutes at 50 ° C. while adjusting the pH to 12.0 with a sodium hydroxide solution, and filtered through 5C filter paper. Further, the residue was washed and filtered with 50 ml of ion-exchanged water and analyzed by ICP. Similarly, the leaching residue of pH 8.0 was immersed in 150 ml of ion exchange water and leached while adjusting to pH 1.5 with a sulfuric acid solution. The above results are shown in Table 2. In the case of the roasted product A, the removal and separation effect of phosphorus is larger at pH 1.5 than at pH 12.0.
On the other hand, in the small roasting product B of mosquitoes Le Siumu was no difference pH12.0 and pH 1.5.

実施例３
表１の焙焼物Ａ、Ｂ各々３０ｇをイオン交換水１５０ｍｌに浸し、水酸化ナトリウム溶液でｐＨ１２.０に調整しながら５０℃で６０分浸出し、５Ｃ濾紙で濾過し、更に、残渣をイオン交換水５０ｍｌで洗浄濾過し、残渣を得た。この残渣をイオン交換水１５０ｍｌに浸し、硫酸溶液でｐＨ１.５に調整しながら浸出し、５Ｃ濾紙で濾過し、更に残渣をイオン交換水５０ｍｌで洗浄濾過し、得られた残渣をＩＣＰ分析した。同様に、上記のｐＨを１.５、２.０として実施した。以上の結果が表２に示されている。焙焼物Ａ及びＢともに、リンの除去分離に差はなかった。また、最もリン含有量の低いニッケル残渣が得られた。 Example 3
30 g of each of the baked products A and B in Table 1 are immersed in 150 ml of ion exchange water, adjusted to pH 12.0 with a sodium hydroxide solution, leached for 60 minutes at 50 ° C., filtered through 5C filter paper, and the residue is ion exchanged. Washing and filtration with 50 ml of water gave a residue. The residue was immersed in 150 ml of ion-exchanged water, leached while adjusting to pH 1.5 with a sulfuric acid solution, filtered through 5C filter paper, the residue was further washed and filtered with 50 ml of ion-exchanged water, and the obtained residue was analyzed by ICP. Similarly, the above pH was set to 1.5 and 2.0. The above results are shown in Table 2. There was no difference in the removal and separation of phosphorus in the baked products A and B. Moreover, the nickel residue with the lowest phosphorus content was obtained.

本発明方法の第１実施例を示す行程図である。It is a process figure which shows 1st Example of the method of this invention. 本発明方法の第２実施例を示す行程図である。It is a process figure which shows 2nd Example of this invention method. 本発明方法の第３実施例を示す行程図である。It is a process figure which shows 3rd Example of this invention method.

Claims (3)

バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をｐＨ６から９の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とした使用済触媒からリン含有物を分離する方法。 Obtained by roasting a spent catalyst using alumina as a carrier used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium at a temperature of 600 ° C or higher. The resulting baked product is acid leached at a pH of 5 or less, filtered, and separated into a nickel-containing residue having a low phosphorus content and a filtrate. Further, the filtrate is adjusted to a pH between 6 and 9, and phosphorus is added. And separating the phosphorus-containing material from the spent catalyst, characterized by neutralizing and precipitating aluminum and the like, and filtering to separate into vanadium and / or molybdenum product starting solution and phosphorus-containing starch . バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ６から９で浸出し、これを濾過して、ニッケル含有残渣とモリブデン及び/又はバナジウム製品化始液とに分離し、前記ニッケル含有残渣をｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、更に、前記濾液をｐＨ６から９の間に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、バナジウム及び/又はモリブデン製品化始液と、リン含有澱物とに分離することを特徴とした使用済触媒からリン含有物を分離する方法。 Obtained by roasting a spent catalyst using alumina as a carrier used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium at a temperature of 600 ° C or higher. The baked product thus obtained was leached at pH 6 to 9, filtered, and separated into a nickel-containing residue and molybdenum and / or vanadium product starting solution. The nickel-containing residue was leached at pH 5 or lower, Is separated into a nickel-containing residue having a low phosphorus content and a filtrate. Further, the filtrate is adjusted to pH 6 to 9 to neutralize and precipitate phosphorus and aluminum. A method for separating a phosphorus-containing material from a spent catalyst, characterized by separating into a vanadium and / or molybdenum product starting solution and a phosphorus-containing starch. バナジウム及びモリブデンの少なくとも一方とニッケルとリンとカルシウムを含む各種石油留分の水素化脱硫に使用されたアルミナを担体とする使用済触媒と、ナトリウム化合物を６００℃以上の温度で焙焼して得られた焙焼物を、ｐＨ１０以上でアルカリ浸出し、これを濾過して、ニッケル含有残渣と濾液とに分離し、更に、前記ニッケル含有残渣をｐＨ５以下で酸浸出し、これを濾過して、リン含有量の低いニッケル含有残渣と濾液とに分離し、前記各濾液をｐＨ６から９に調整して、リン及びアルミニウム等を中和沈澱させ、これを濾過して、モリブデン及び/又はバナジウム製品化始液と、リン含有澱物とに分離することを特徴とした使用済触媒からリン含有物を分離する方法。 Obtained by roasting a spent catalyst using alumina as a carrier used for hydrodesulfurization of various petroleum fractions containing at least one of vanadium and molybdenum, nickel, phosphorus and calcium , and a sodium compound at a temperature of 600 ° C or higher. the resulting roasted material, alkali leaching at pH10 or more, which was filtered and separated into a nickel-containing residue and filtrate, further, the acid-leached nickel containing residue at pH5 or less, which was filtered, phosphorus Separated into nickel-containing residue and filtrate with low content, each of the filtrates was adjusted to pH 6 to 9 to neutralize and precipitate phosphorus, aluminum, etc., and filtered to obtain molybdenum and / or vanadium products. A method for separating a phosphorus-containing material from a spent catalyst, characterized in that it is separated into a liquid and a phosphorus-containing starch.
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